Manganese oxide nanowires, films, and membranes and methods of making

ABSTRACT

Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves, and methods of making, are disclosed. A single crystal ultra-long nanowire includes an ordered porous manganese oxide-based octahedral molecular sieve, and has an average length greater than about 10 micrometers and an average diameter of about 5 nanometers to about 100 nanometers. A film comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is stacked on a surface of a substrate, wherein the nanowires of each layer are substantially axially aligned. A free standing membrane comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is aggregately stacked, and wherein the nanowires of each layer are substantially axially aligned.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application relates to, and claims the benefit of, U.S.Provisional Patent Application No. 60/607,496, which was filed on Sep.3, 2004 and is incorporated herein in its entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

The U.S. Government has certain rights in this invention pursuant toDepartment of Energy Grant No. DE-FG02-86ER13662.A0000.

BACKGROUND

Inorganic materials that have unusual structures often exhibitinteresting chemical and physical characteristics which find extensiveapplications in diverse fields. For example, inorganic molecular sievesare porous crystalline structures comprising a solid three-dimensionalframework with interconnected internal cavities or pores. Applicationsfor these materials include ion, molecule, and gas separations; moleculeand gas sensing; ion-exchange; and catalysis, among others.

Ordered porous manganese-based octahedral molecular sieves (OMS)constitute an exemplary class of molecular sieves. These materials haveone-dimensional tunnel structures and unlike zeolites, which havetetrahedrally coordinated species serving as the basic structural unit,these materials are based on six-coordinate manganese surrounded by anoctahedral array of anions (e.g., oxide). The OMS framework architectureis dictated by the type of aggregation (e.g., corner-sharing,edge-sharing, or face-sharing) of the MnO₆ octahedra. The ability ofmanganese to adopt multiple oxidation states and of the MnO₆ octahedrato aggregate in different arrangements affords the formation of a largevariety of OMS structures.

Many commercial applications have traditionally used molecular sieves inthe form of granules or pellets. Recently, films or membranes ofmolecular sieves have gained considerable importance as alternatives togranules or pellets. However, suitable inorganic oxide-based materialsare difficult to prepare as films or membranes owing to theirbrittleness and poor mechanical properties. A variety of molecularmaterials, mostly organic polymers, have been found to be suitable foruse as membranes. However, organic polymer membranes have relativelyshort service lives because of their sensitivity to solvents and lowstability at high temperatures.

There accordingly remains a need in the art for new methods of preparinginorganic oxide-based molecular sieve films or membranes because oftheir superior thermal and chemical properties to organic polymers. Itwould be particularly advantageous if such methods could eliminate orresult in decreased brittleness. It would be further advantageous ifsuch methods could result in increased mechanical properties forprocessing the films or membranes.

SUMMARY

A method for forming nanowires includes hydrothermally treating achemical precursor composition in a hydrothermal treating solvent toform the nanowires, wherein the chemical precursor composition comprisesa source of manganese cations and a source of counter cations, andwherein the nanowires comprise ordered porous manganese oxide-basedoctahedral molecular sieves.

A single crystal ultra-long nanowire comprises an ordered porousmanganese oxide-based octahedral molecular sieve, wherein the singlecrystal ultra-long nanowire has an average length greater than about 10micrometers and an average diameter of about 5 nanometers to about 100nanometers.

A film includes a microporous network comprising a plurality of singlecrystal nanowires in the form of a layer, wherein a plurality of layersis stacked on a surface of a substrate, wherein the nanowires compriseordered porous manganese oxide-based octahedral molecular sieves andhave average lengths greater than about 10 micrometers and substantiallyuniform average diameters of about 5 nanometers to about 100 nanometers,and wherein the nanowires of each layer are substantially axiallyaligned.

A free standing membrane comprises a microporous network comprising aplurality of single crystal nanowires in the form of a layer, wherein aplurality of layers is aggregately stacked, wherein the nanowirescomprise ordered porous manganese oxide-based octahedral molecularsieves and have average lengths greater than about 10 micrometers andsubstantially uniform average diameters of about 5 nanometers to about100 nanometers, and wherein the nanowires of each layer aresubstantially axially aligned.

BRIEF DESCRIPTION OF THE DRAWINGS

Referring now to the Figures, which are exemplary embodiments, andwherein the like elements are numbered alike:

FIG. 1 is a powder X-ray diffraction pattern of a K—OMS-2 film;

FIG. 2 is a transmission electron micrograph of a bundle of K—OMS-2fibers with a selected area electron diffraction pattern of a singlenanowire;

FIG. 3 is a scanning electron micrograph of a K—OMS-2 membrane grown ona patterned substrate;

FIG. 4 is a scanning electron micrograph of a K—OMS-2 membrane withAu-nanoparticles embedded within the empty spaces of the aggregatednanowires, shown at 20000 times magnification;

FIG. 5 is a scanning electron micrograph of a K—OMS-2 membrane withcarbon nanotubes embedded within the empty spaces of the aggregatednanowires, shown at 50000 times magnification; and

FIG. 6 is a scanning electron micrograph of a K—OMS-2 membrane withSn—Sb—Pb—Hg nano-alloy particles embedded within the empty spaces of theaggregated nanowires, shown at 50000 times magnification.

DETAILED DESCRIPTION

Disclosed herein are methods for making nanowires, films, and membranescomprising ordered porous octahedral molecular sieves (OMS) based onmanganese oxides. A method for making the nanowires generally compriseshydrothermally treating a chemical precursor composition to form thenanowires, wherein the chemical precursor composition comprises a sourceof manganese cations and a source of counter cations. A film generallymay be formed from the nanowires by forming a suspension of thenanowires, and contacting the suspension with a substrate at a time anda temperature effective to self-assemble the film comprising thenanowires. A membrane generally may be formed by removing the substratefrom the film. The nanowires, films, and membranes produced by themethods disclosed herein are advantageously less brittle and/or moremechanically robust than those made by methods of the prior art.

The term “nanowire” has its ordinary meaning as used herein, andgenerically describes a material that has a wire-like structure with anaverage diameter of about 1 to about 500 nanometers (nm) and an aspectratio greater than about 10. As used herein, a “film” includes acombination of nanowires deposited on a surface of a substrate. The term“substrate” is used herein in its broadest sense, and includes materialshaving irregular shapes such as for example flakes, as well as regularshapes such as for example spheres, sheets, and films upon which thefilm may be produced. The term “self-assemble” as used herein refers toformation of a material (e.g., the film) without application of anyexternal forces other than heat. As used herein, the terms “membrane”and “free standing membrane” (FSM) are meant to be used interchangeablyand generically describe the film detached from the substrate.

Also as used herein, the terms “first,” “second,” and the like do notdenote any order or importance, but rather are used to distinguish oneelement from another, and the terms “the”, “a” and “an” do not denote alimitation of quantity, but rather denote the presence of at least oneof the referenced item. Furthermore, all ranges reciting the samequantity or physical property are inclusive of the recited endpoints andindependently combinable. The modifier “about” used in connection with aquantity is inclusive of the stated value and has the meaning dictatedby the context or includes the degree of error associated withmeasurement of the particular quantity.

In one embodiment, the OMS materials produced by the methods disclosedherein are todorokites. Todorokites include materials wherein the MnO₆octahedra share edges to form triple chains and the triple chains sharecorners with adjacent triple chains to form a 3×3 tunnel structure. Thesize of an average dimension of these tunnels is about 6.9 Angstroms(Å). A counter cation, for maintaining overall charge neutrality, suchas Na, Ca, Mg, and the like is present in the tunnels and is coordinatedto the oxides of the triple chains. Todorokites are generallyrepresented by the formula (M)Mn₃O₇, wherein M represents the countercation and manganese is present in at least one oxidation state.Further, the formula may also include waters of hydration and isgenerally represented by (M)_(y)Mn₃O₇.xH₂O, where y is about 0.3 toabout 0.5 and x is about 3 to about 4.5.

In one embodiment, the OMS materials produced by the methods disclosedherein are hollandites. Hollandites include a family of materialswherein the MnO₆ octahedra share edges to form double chains and thedouble chains share corners with adjacent double chains to form a 2×2tunnel structure. The size of an average dimension of these tunnels isabout 4.6 Å. A counter cation for maintaining overall charge neutralitysuch as Ba, K, Na, Pb, and the like, is present in the tunnels and iscoordinated to the oxides of the double chains. The identity of thecounter cation determines the mineral species or structure type.Hollandites are generally represented by the formula (M)Mn₈O₁₆, whereinM represents the counter cation and manganese is present in at least oneoxidation state. Further, the formula may also include waters ofhydration and is generally represented by (M)_(y)Mn₈O₁₆.xH₂O, where y isabout 0.8 to about 1.5 and x is about 6 to about 10. Suitablehollandites include hollandite (BaMn₈O₁₆), cryptomelane (KMn₈O₁₆),manjiroite (NaMn₈O₁₆), coronadite (PbMn₈O₁₆), and the like, and variantsof at least one of the foregoing hollandites. In one embodiment, the OMSmaterials produced are cryptomelane-type materials.

Hereinbelow, an OMS material with a 3×3 tunnel structure, such as in thetodorokites, will be referred to by the designation “M-OMS-1”, and anOMS material with a 2×2 tunnel structure, such as in the hollandites,will be referred to by the designation “M-OMS-2”, wherein M representsthe appropriate counter cation.

Suitable precursor compositions comprise a source of manganese cationsand a source of counter cations. The source of manganese cations may beany inorganic or organic manganese-containing compound, provided thatthe compound does not substantially interfere with other components ofthe chemical precursor composition or the course of the reaction.Further, the manganese may be in any of its known oxidation states.Suitable compounds include manganese salts, including but not limited tothose with an anion such as sulfate; persulfate; sulfide; nitrite;nitrate; phosphate; halide such as fluoride, chloride, bromide, andiodide; perchlorate; carbonate; acetate; alkoxide such as for examplemethoxide, ethoxide, propoxide; dichromate; formate; chromate; oxalate;acetate; and the like. Manganese salts containing a combinationcomprising at least one of the foregoing anions may be used, as well ascombinations of different manganese salts. Hydrates of manganese saltsmay also be used, for example a hydrate of one of the foregoing salts,or a combination comprising a hydrate of at least one of the foregoingsalts. Mixtures of hydrates and non-hydrates may also be used. In oneembodiment, the source of manganese cations is manganese sulfatemonohydrate.

The counter cations may be any alkali metal, alkaline earth metal,transition metal, rare earth metal, main group metal, or complex cationin a +1, +2, +3, and/or +4 oxidation state. Suitable counter cationsinclude cations of H, Li, K, Rb, Cs, Ba, Mg, Ca, Pb, Co, Ni, Cu, Fe, V,Nb, Ta, Cr, Mo, Ag, W, Zr, Ti, Cd, Zn, Ln (wherein Ln is lanthanum orany of the lanthanides), or ammonium counter cations. The source ofcounter cations may be any inorganic or organic compound, provided thatthe compound does not substantially interfere with other components ofthe chemical precursor composition or the course of the reaction.Suitable compounds include manganese salts, including but not limited tothose with an anion such as sulfate; persulfate; sulfide; nitrite;nitrate; phosphate; halide such as fluoride, chloride, bromide, andiodide; perchlorate; carbonate; acetate; alkoxide such as for examplemethoxide, ethoxide, propoxide; dichromate; formate; chromate; oxalate;acetate; and the like. Counter cation salts containing a combinationcomprising at least one of the foregoing anions may be used, as well asa combination of different counter cation salts. Hydrates of countercation salts may also be used, for example a hydrate of one of theforegoing salts, or a combination comprising a hydrate of at least oneof the foregoing salts. Mixtures of hydrates and non-hydrates may alsobe used. In one embodiment, the source of counter cations is potassiumsulfate and potassium persulfate. In another embodiment, the source ofcounter cations is ammonium sulfate and ammonium persulfate. It ispossible to use mixed salts, that is, salts that provide more than onetype of counter cation, but generally, where more than one type ofcounter cation is desired in the nanowire, the precursor compositionwill comprise a separate source for each counter cation.

Optionally, the chemical precursor composition may further comprise asource of a framework substituting cation, wherein a frameworksubstituting cation is a cation other than manganese present in theframework in place of a portion of the manganese. Similar to themanganese, the framework substituting cation may be present in theframework in more than one oxidation state. Suitable frameworksubstituting cations include cations of H, Li, K, Rb, Cs, Ba, Mg, Ca,Pb, Co, Ni, Cu, Fe, V, Nb, Ta, Cr, Mo, Ag, W, Zr, Ti, Cd, Zn, or Ln.Desirably, the framework substituting cations are cations of Cu, Fe, Co,or Ni. The source of a framework substituting cation is present in anamount effective to introduce the desired proportions of the frameworksubstituting cation into the framework of the OMS during the course ofthe reaction. The source of the framework substituting cation may be anyinorganic or organic compound, provided that the compound does notsubstantially interfere with other components of the chemical precursorcomposition or the course of the reaction. Suitable compounds includeframework substituting salts, including but not limited to those with ananion such as sulfate; persulfate; sulfide; nitrite; nitrate; phosphate;halide such as fluoride, chloride, bromide, and iodide; perchlorate;carbonate; alkoxide such as for example methoxide, ethoxide, propoxide;dichromate; formate; chromate; oxalate; acetate; and the like. Frameworksubstituting salts containing a combination comprising at least one ofthe foregoing anions may be used, as well as a combination of differentframework substituting salts. Hydrates of framework substituting saltsmay also be used, for example a hydrate of one of the foregoing salts,or a combination comprising a hydrate of at least one of the foregoingsalts. Mixtures of hydrates and non-hydrates may also be used. It ispossible to use mixed salts, that is, salts that provide more than onetype of framework substituting cation, but generally, where more thanone type of framework substituting cation is desired in the nanowire,the precursor composition will comprise a separate source for eachframework substituting cation.

Hydrothermally treating the chemical precursor composition comprisesheating the chemical precursor composition and a solvent in a sealedreaction vessel. The solvent used in the hydrothermal treating maycomprise any aqueous or organic compound that is liquid at the reactiontemperature, provided that the liquid does not substantially interferewith the course of the reaction. Suitable solvents include water, suchas tap water, deionized water (DI—H₂O), distilled water, or deionizeddistilled water (DDW); acids, such as nitric acid, acetic acid, sulfuricacid, phosphoric acid, hydrofluoric acid, and the like; bases, such ashydroxides of Na, K, NH₄, and the like; alcohols; and the like and acombination comprising at least one of the foregoing solvents. In oneembodiment, the hydrothermal treating solvent is DDW.

The reaction vessel may be of any size and composition that permitsapplication and/or development of pressure, and further permits controlof temperature and agitation of its contents. In one embodiment, thereaction vessel comprises interior facing walls formed of an inertmaterial. The inert material is selected such that it is inert to theprecursor composition and the solvent, and withstands the temperatureand pressure of heating. In one embodiment the inert material is afluorinated polymer. Suitable fluorinated polymers includetetrafluoroethylene (TFE), polytetrafluoroethylene (PTFE),fluoro(ethylene-propylene) (FEP), and the like.

The temperature, pressure, and time of the hydrothermal treatment affectnanowire growth rate as well as product formation and yield, and mayvary depending on the desired size and product yield. Suitableconditions may be determined by one of ordinary skill in the art withoutundue experimentation using the guidelines provided herein. The heatingtemperature has a greater effect on nanowire crystallization, while theheating time has a greater effect on nanowire size. The crystallizationrate increases with heating temperature and nanowire size increases withheating time. In one embodiment, the temperature of heating is about 150to about 350 degrees Celsius (° C.). In another embodiment, thetemperature of heating is about 200 to about 300° C. In yet anotherembodiment, the temperature of heating is about 225 to about 275° C.Pressures of about 1 to about 100 atmospheres (atm) are obtained.Typically, the time of the hydrothermal treatment is greater than about12 hours and is dependent on the desired nanowire size. The heating timeof the hydrothermal treatment may be greater than about 18 hours.

After the hydrothermal treatment, the nanowires may be isolated byremoving the contents of the sealed reaction vessel, rinsing, andfiltering.

In one advantageous feature, the nanowires produced by the method aresingle crystals and have substantially uniform diameters, wherein thevariation in diameter is less than about 1%. In one embodiment, theaverage nanowire diameters are about 5 to about 100 nm. In anotherembodiment, the average nanowire diameters are about 10 to about 50 nm.

In another advantageous feature, the nanowires produced by the methodare ultra-long nanowires. The ultra-long nanowires have average lengthsof greater than about 10 micrometers. In another embodiment, theultra-long nanowires have average lengths greater than about 100micrometers. In yet another embodiment, the ultra-long nanowires haveaverage lengths greater than about 500 micrometers. In yet anotherembodiment, the ultra-long nanowires have average lengths greater thanabout 1 millimeter (mm). In yet another embodiment, the ultra-longnanowires have average lengths greater than about 10 mm.

In another advantageous feature, the nanowires produced by the methodhave micropores, mesopores, and/or macropores. Further, the tensilestrengths of the nanowires and the conductivity of the nanowires may bequite high.

In one embodiment, the nanowires are aggregated to form a ropecomprising several strands of nanowires. In another embodiment, thenanowires may be shaped and/or wrapped around various objects.

In one embodiment, after the hydrothermal treatment, the isolatednanowires may be subjected to an optional ion exchange step, wherein aportion or all of the counter cations may be replaced with differentcounter cations. The ion exchange step may be any effective ion exchangestep as known to those skilled in the art, for example a secondhydrothermal treatment similar to that described above, a thermaltreatment, a thermal oxidation treatment, or the like.

In one embodiment, a foreign material, for example a particle, may beembedded within a pore of a nanowire. The foreign material can beanything that is not integral to the framework of the nanowire. Suitableforeign materials include metals, alloys, organic molecules, polymers,enzymes, ceramics, glasses, and the like, and combinations comprising atleast one of the foregoing materials.

To produce the film, a suspension is formed by placing the nanowires ina suspension solvent. The suspension solvent may comprise any aqueous ororganic liquid that does not adversely affect the structure orproperties of the nanowires. Suitable suspension solvents include, butare not limited to, water, such as tap water, DI—H₂O, distilled water,DDW; acids, such as nitric acid, acetic acid, sulfuric acid, phosphoricacid, hydrofluoric acid, and the like; bases, such as hydroxides of Na,K, NH₄, and the like; alcohols; and the like, and combinationscomprising at least one of the foregoing solvents. The suspensionsolvent may or may not be the same as the hydrothermal treating solvent.In one embodiment, the suspension solvent is DDW.

Formation of the suspension may be facilitated by agitation. Agitationmay be in the form of stirring or sonication. In another embodiment, theformation of the suspension may be facilitated through heating.Desirably, the suspension is substantially homogeneous.

The film is self-assembled by heating the suspension, without agitation,in the presence of the substrate. Suitable conditions for the time andtemperature of self-assembly may be determined by one of ordinary skillin the art without undue experimentation using the guidelines providedherein. The temperature of self-assembly may be about 50 to about 150°C., specifically about 70 to about 100° C. The time of self-assembly isgenerally greater than about 6 hours, specifically greater than about 12hours.

The substrate may be any solid material with a surface on which the filmwill self-assemble. Suitable substrates include metals, alloys,ceramics, glass, organic polymers, fluorinated polymers, quartz,sapphire, wood, paper, and the like. Suitable metals include transitiongroup metals, rare earth metals including lanthanides and actinides,alkali metals, alkaline earth metals, main group metals, andcombinations comprising at least one of the foregoing metals. Suitablefluorinated polymers include TFE, PTFE, FEP, and the like. In onespecific embodiment, the substrate is PTFE.

The shape of the substrate does not appear to be critical. In oneembodiment, the substrate is stamped with a pattern and the film adoptsthe pattern of the stamped substrate.

In one advantageous feature, more than one substrate may be used toself-assemble more than one film simultaneously.

While not wishing to be bound by theory, it is believed that theself-assembly of the nanowires on the substrate to form the film dependson factors such as substrate surface tension and convection, as well asnanowire-substrate surface and nanowire-nanowire interactions. Theself-assembly process proceeds via convection of tangled nanowires fromthe bottom to the top of the vessel containing the substrate and thesuspension. During evaporation of the suspension solvent, liquid isexpelled from the suspension containing the nanowires and a clearerphase appears at the bottom of the vessel. The expulsion is believed tobe driven by interfacial tension processes, which continue to reduce thesurface area of the suspension to minimize its energy.

The removing of the substrate from the film to form the FSM may comprisepeeling, cutting, or dissolving the substrate. After the FSM is formed,it may undergo annealing. A temperature for the annealing step is about80 to about 200° C. for a duration greater than about one hour.

The film and the membrane comprise a microporous network of nanowires. Alayer is formed from a plurality of nanowires that are substantiallyaxially aligned and a plurality of layers is aggregately stacked. In oneembodiment, the nanowires in each layer may be essentially parallel toeach other. In another embodiment, the layers are stacked with a changein direction of nanowire orientation of about 90° at every layer. It isbelieved that the film, and the membrane, have three levels ofstructure: a primary structure with each fiber as a microporousstructure (tunnels); a secondary mesoscopic assembly of long nanowiressubstantially axially aligned to form a layer; and a tertiarymacroscopic structure, which results from the alignment and connectivityof the microporous network to form the membrane in the absence ofexternal forces. The porosity leads to an enhancement of texturalproperties of the membrane. For example, the surface area of themembrane is about 10 to about 500 squared meters per gram (m²/g).

It is believed that the thickness of the film, and of the membrane, maybe controlled by the dimension of the substrate and by the concentrationof the suspension. The average thickness of the film (not including thesubstrate), and of the membrane, may be about 1 micrometer to about 10mm.

In one advantageous feature, the membrane produced by the method isrobust, flexible, and resilient to bending. The membrane may be writtenon, folded and/or cut into various shapes while remaining intact. A roomtemperature tensile strength of the membrane is about 0.1 to about 10megaPascals (MPa). Further, the membrane also maintains its malleabilityunder cryogenic conditions.

In another advantageous feature, the membrane may be “recycled” and anew membrane may be formed by re-submerging the membrane into the secondsolvent and by simply repeating the film self-assembly process offorming a suspension and heating the suspension in the presence of thesubstrate.

In yet another advantageous feature, the film and/or the membrane maycomprise embedded materials within the empty spaces of the aggregatednanowires. Suitable embedded materials include metals, alloys, organicmolecules, polymers, catalysts, enzymes, ceramics, glasses, and thelike, and a combination comprising at least one of the foregoingmaterials.

The nanowires, films and/or FSM are useful in a variety of applicationsincluding, but not limited to, ion, molecule, and gas separations;molecule and gas sensing; ion-exchanging; semiconductors;photocatalysis; heterogeneous catalysis; and lithium secondary batterycathodes among others.

The invention is further illustrated by the following non-limitingexamples.

In these examples, characterization of products was carried out usingseveral techniques. The phase of each product was identified by powderX-ray diffraction (PXRD) using a Scintag XDS-2000 diffractometer withCuKα radiation operating at 45 kV and 40 mA. The chemical compositionwas determined by inductively coupled plasma atomic emissionspectroscopy (ICP) and thermogravimetric analysis (TGA). An averageoxidation state (AOS) of manganese was determined by potentiometrictitration methods. A room temperature conductivity was determined usingfour-probe techniques. A BET surface area was measured by N₂ desorptionusing a BJH model.

The cross-sectional area of film and membrane samples were studied byfield emission scanning electron microscopy (FESEM) using a Zeiss DSM982 Gemini microscope with a Schottky Emitter operated at 2 kV with abeam current of about 1 μA. Cross-sectional samples of the paper-likematerial were prepared by carefully cutting the material with a sharpknife. The sample was then deposited horizontally on carbon tape. A 45°stub holder was used for the study and the samples were tilted 45°towards the edge in order to bring the cross-sectional area of thesample to focus.

High-resolution transmission electron microscopy (HRTEM) studies of theflat surface and cross-sectional area of membrane samples were carriedout using a JEOL 2010 FasTEM at an accelerating voltage of 200 kV. Aflat sample was prepared by cutting 3 mm segments of the sample andgluing it to a slotted cooper grid. The sample was then ion milled usinga precision ion polishing system (PIPS). For the cross-sectionalstudies, the sample was supported between two silicon wafers and held inplace with M-Bond adhesive (TEM grade). The “sandwich” was mechanicallyground to a diameter of 2 mm and a thickness of about 0.75 mm. Thesample was then placed inside a 3 mm (OD) brass tube and filled withGatan G-1 Resin. The tube was subsequently sliced, ground, and thinnedin the same way as the flat sample.

EXAMPLE 1 K—OMS-2

The chemical precursor compositions, 19.1 millimoles (mmol) of K₂SO₄,K₂O₈S₂, and MnSO₄.H₂O in a 3:3:2 ratio, were dissolved in 80 milliliters(mL) DDW. The chemical precursor compositions and the solvent weretransferred to a Teflon-lined stainless steel vessel. The vessel wassealed and placed in an oven and heated at 250° C. for 4 days to produceK—OMS-2 nanowires. The nanowires were suspended in 800 mL of DDW andstirred vigorously overnight, producing a stable wool-like homogeneoussuspension. A dark brown K—OMS-2 film, as evidenced by the PXRD patternof FIG. 1, was then produced by heating the suspension at 85° C. for 24hours in the presence of a Teflon substrate.

Scanning and transmission electron microscopy show that the FSMcomprised long nanowires with uniform diameter of about 30 nm. Electrondiffraction of individual nanowires, as seen in FIG. 2, demonstratesthat the nanowires were single crystals. The composition of the K—OSM-2FSM was K₃Mn_(7.95)O_(16.20).0.51H₂O. The conductivity was about 0.53Siemens/centimeter (S/cm) and is one order of magnitude better than thatof bulk cryptomelane-like materials. The tensile strength was about 6MPa and the surface area was about 39 m²/g.

EXAMPLE 2 Stamped Substrate K—OMS-2

A K—OSM-2 FSM was prepared according to Example 1, except that a stampedsubstrate was used. As shown in FIG. 3, the FSM adopted the pattern ofthe stamped substrate.

EXAMPLE 3 NH₄—OSM-2

An NH₄—OSM-2 was prepared according to Example 1, except the K₂SO₄ andK₂O₈S₂ were substituted with (NH₄)₂SO₄ and (NH₄)₂O₈S₂. The diameter ofthe NH₄—OSM-2 nanowires was about 30 nm. Electron diffraction ofindividual nanowires also demonstrates that the nanowires were singlecrystals. The conductivity was about 0.22 S/cm, the tensile strength wasabout 0.25 MPa, and the surface area was about 36 m²/g.

EXAMPLE 4 Hydrothermal Ion Exchange of NH₄—OSM-2

NH₄—OSM-2 nanowires were synthesized according to Example 3. 5 samplesof NH₄—OSM-2 nanowires were mixed with LiOH, NaOH, KOH, RbOH, and CsOHin DDW and placed in separate Teflon-lined stainless steel vessel. Eachvessel was sealed and placed in an oven and heated at 250° C. for 4 daysto produce OMS-2 nanowires where the NH₄ ⁺ counter cation was replacedby Li⁺, Na⁺, K⁺, Rb⁺, and Cs⁺, respectively.

Electron microscopy indicated that the overall lengths of the nanowireshad decreased about 30% upon undergoing the ion exchange step. In oneexample, the conductivity of Li—OMS-2 was about 0.01 S/cm.

EXAMPLE 5 Thermal Ion Exchange and Oxidation of NH₄—OSM-2

NH₄—OSM-2 nanowires were synthesized according to Example 3. A sample ofNH₄—OSM-2 nanowires was added to a mixture of concentrated HNO₃ andH₂SO₄ under reflux at 90° C. for 2 hours. The product was then rinsedwith DI—H₂O. The NH₄ ⁺ ions were partially replaced by H⁺ ions. Uponheating in an oven at 75° C. for 12-24 hours, however, fully exchangedH—OMS-2 nanowires were formed. The conductivity of H—OMS-2 wasdetermined to be about 0.02 S/cm.

EXAMPLE 6 Recycled K—OMS-2 Membrane

K—OMS-2 FSM was prepared according to Example 1. The FSM was placed inDI—H₂O, or a 1 M solution of LiNO₃, and stirred vigorously for 4 hoursto produce a stable homogeneous suspension. Another dark brown K—OMS-2film was produced by re-heating the suspension at 85° C. for 24 hours inthe presence of a Teflon substrate.

The properties of the recycled K—OMS-2 remained substantially the sameas in Example 1.

EXAMPLE 7 Embedded Nanoparticles in K—OMS-2 FSM

K—OSM-2 nanowires were synthesized according to Example 1. Samples ofsuspensions of Au nanoparticles, Pt nanoparticles, carbon nanotubes, andSn—Sb—Pb—Hg nano-alloys, were individually added along with thenanowires to DDW and stirred vigorously overnight, producing ahomogeneous suspension. The suspensions were heated at 85° C. for 24hours in the presence of a PTFE substrate to produce embeddednanoparticles-K—OSM-2 FSM.

FIGS. 4-6 show K—OSM-2 FSM with Au-nanoparticles, carbon nanotubes, andSn—Sb—Pb—Hg nano-alloy particles, respectively, embedded within theempty spaces of the aggregated nanowires.

While the invention has been described with reference to exemplaryembodiments, it will be understood by those skilled in the art thatvarious changes may be made and equivalents may be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications may be made to adapt a particular situationor material to the teachings of the invention without departing from theessential scope thereof. Therefore, it is intended that the inventionnot be limited to the particular embodiment disclosed as the best modecontemplated for carrying out this invention, but that the inventionwill include all embodiments falling within the scope of the appendedclaims.

1. A film, comprising a microporous network comprising a plurality ofsingle crystal nanowires in the form of a layer, wherein a plurality oflayers is stacked on a surface of a substrate, wherein the nanowirescomprise ordered porous manganese oxide-based octahedral molecularsieves and have average lengths greater than about 10 micrometers andsubstantially uniform average diameters of about 5 nanometers to about100 nanometers, and wherein the nanowires of each layer aresubstantially axially aligned.
 2. The film of claim 1, furthercomprising a change in a direction of a nanowire orientation of about90° between each layer of the plurality of layers.
 3. The film of claim1, wherein a counter cation of the ordered porous manganese oxide-basedoctahedral, molecular sieves comprises a cation of H, Li, K, Rb, Cs, Ba,Mg, Ca, Pb, Co, Ni, Cu, Fe, V, Nb, Ta, Cr, Mo, Ag, W, Zr, Ti, Cd, Zn,Ln, ammonium, or a combination comprising at least one of the foregoingcations.
 4. The film of claim 1, further comprising a frameworksubstituting cation, wherein the framework substituting cation of theordered porous manganese oxide-based octahedral molecular sievescomprises a cation of H, Li, K, Rb, Cs, Ba, Mg. Ca, Pb, Co, Ni, Cu, Fe,V, Nb, Ta, Cr, Mo, Ag, W, Zr, Ti, Cd, Zn, Ln, or a combinationcomprising at least one of the foregoing cations.
 5. The film of claim1, wherein the substrate is stamped with a pattern and the film adoptsthe pattern of the stamped substrate.
 6. The film of claim 1, wherein anaverage thickness of the film, not including the substrate, is about 1micrometer to about 1.0 millimeters.
 7. The film of claim 1, wherein asurface area of the film is about 10 squared meters per gram to about500 squared meters per gram.
 8. The film of claim 1, further comprisinga metal, alloy, organic molecule, polymer, catalyst, enzyme, ceramic,glass, or a combination comprising at least one of the foregoing,embedded within an empty space of the microporous network.
 9. A freestanding membrane, comprising a microporous network comprising aplurality of single crystal nanowires in the form of a layer, wherein aplurality of layers is aggregately stacked, wherein the nanowirescomprise ordered porous manganese oxide-based octahedral molecularsieves and have average lengths greater than about 10 micrometers andsubstantially uniform average diameters of about 5 nanometers to about100 nanometers, and wherein the nanowires of each layer aresubstantially axially aligned.
 10. The free standing membrane of claim9, further comprising a change in direction of a nanowire orientation ofabout 90° between each layer of the plurality of layers.
 11. The freestanding membrane of claim 9, wherein a counter cation of the orderedporous manganese oxide-based octahedral molecular sieves comprises acation of H, Li, K, Rb, Cs, Ba, Mg, Ca, Pb, Co, Ni, Cu, Fe, V,Nb, Ta,Cr, Mo, Ag, W, Zr, Ti, Cd, Zn, Ln, ammonium, or a combination comprisingat least one of the foregoing cations.
 12. The free standing membrane ofclaim 9, further comprising a framework substituting cation, wherein theframework substituting cation of the ordered porous manganeseoxide-based octahedral molecular sieves comprises a cation of H, Li, K,Rb, Cs, Ba, Mg, Ca, Pb, Co, Ni, Cu, Fe, V, Nb, Ta, Cr, Mo, Ag, W, Zr,Ti, Cd, Zn, Ln, or a combination comprising at least one of theforegoing cations.
 13. The free standing membrane of claim 9, wherein anaverage thickness of the free standing membrane is about 1 micrometer toabout 10 millimeters.
 14. The free standing membrane of claim 9, whereina surface area of the free standing membrane is about 10 squared metersper gram to about 500 squared meters per gram.
 15. The free standingmembrane of claim 9, further comprising a metal, alloy, organicmolecule, polymer, catalyst, enzyme, ceramic, glass, or a combinationcomprising at least one of the foregoing, embedded within an empty spaceof the microporous network.
 16. The free standing membrane of claim 9,wherein a tensile strength of the free standing membrane is about 0.1megaPascals to about 10 megaPascals.
 17. The free standing membrane ofclaim 9, wherein the free standing membrane may be patterned, writtenon, folded, cut into a shape, or a combination comprising at least oneof the foregoing, while remaining essentially intact.